KR101088613B1 - Wear-resistant optical layers and moulded bodies - Google Patents

Abstract

Nanoparticles having surface modifications and surface-modified organic radicals with groups having active hydrogen or precursors thereof, in particular hydroxyl groups and / or epoxy groups, and at least one isocyanate which may be blocked by isocyanate groups A composition is disclosed.

Molded or coated substrates obtainable by the composition exhibit high transparency and high wear resistance and are therefore particularly suitable for optical applications.

Active hydrogen, nanoscale solid particles, isocyanate

Description

Wear-resistant optical layer and molded body {WEAR-RESISTANT OPTICAL LAYERS AND MOULDED BODIES}

The present invention provides surface modified nanoscale solid particles and one or more optionally blocked groups having active hydrogens or precursors thereof, preferably having hydroxyl groups and / or epoxy groups. A composition comprising a blocked isocyanate compound and a coating layer and molding that can be prepared from the composition and cured to form a urethane bond or a corresponding bond.

Highly transparent layers for optical components or attrition-resistant layers for optical components have been an important area of research. Nanocomposite coatings based on the sol-gel method have been found to be important, in which organosilanes are cocondensed with the nanoparticles to form a rigid layer. When using silanes containing polymerizable groups (methacrylates or epoxides) such layers may also be UV-curable and photostructurable. However, a disadvantage of such coating layers is the lack of UV stability and also insufficient scratch resistance associated with high brittleness.

Accordingly, it is an object of the present invention to provide a coating layer or molding having high transparency and further showing high wear resistance.

Surprisingly, it is an object of the present invention to provide solid particles which are surface-modified nanoscale, having organic radicals on the surface with groups having active hydrogen or precursors thereof, preferably having hydroxyl groups and / or epoxy groups, And is achieved by a composition comprising at least one isocyanate (the above isocyanate groups may be blocked).

Curing of the composition forms a high optical quality layer or molding that can be used, for example, in the coating of lenses and other optical moldings. Surprisingly, the abrasion test shows that such layers have up to 20 times improved wear resistance compared to similar polyurethanes without the nanoscale solid particles used according to the present invention. For example, conventional polyurethanes without nanoparticles produce abrasion resistance of approximately 40 mg weight loss according to the standard Taber test, while the nanoparticle-containing polyurethanes of the present invention The layer exhibits wear resistance up to 2 mg according to the standard Taber abrader test.

The composition includes surface-modified nanoscale solid particles. The nanoscale solid particles (hereinafter also referred to as nanoparticles) may be, for example, organic particles made of plastic, or preferably inorganic nanoparticles. The nanoparticles are preferably made of metals, for example metal alloys, metal compounds, in particular metal chalcogenides, more preferably oxides and sulfides, and semiconductor compounds do. One type of nanoscale solid particles or a mixture of different nanoscale solid particles can be used.

Examples of metal nanoparticles include copper, silver, gold, platinum, palladium, nickel, chromium and titanium, and also alloys containing these metals, such as (stainless) steel, brass and bronze. There are things that are manufactured.

Examples of nanoparticles that may have semiconductor properties are those made of silicon or germanium. In addition, some of the following metal compounds, such as compounds of elements of the Periodic Tables III and V (eg GaAs or InP), compounds of transition metals Group II and VI elements (eg O, S, Compounds of Se or Te and Zn or Cd, or mixed oxides (for example metal tin oxides such as indium tin oxide (ITO), antimony tin oxide (ATO) or fluorine-doped tin oxide) -doped tin oxide (FTO)) may have semiconductor properties. Materials having semiconductor properties are known to those skilled in the art and examples can also be found in the list below.

Nanoscale inorganic solid particles can be made of any metal compounds, where the metal comprises silicon and boron. Examples of (optionally hydrated) oxides such as ZnO, CdO, SiO ₂ , GeO ₂ , TiO ₂ , ZrO ₂ , CeO ₂ , SnO ₂ , Al ₂ O ₃ (especially boehmite) , AlO (OH), also in the form of aluminum hydroxide), B ₂ O ₃ , In ₂ O ₃ , La ₂ O ₃ , Fe ₂ O ₃ , Fe ₃ O ₄ , Cu ₂ O, Ta ₂ O ₅ , Nb ₂ O ₅ , V ₂ O ₅ , MoO ₃ or WO ₃ ; Further chalcogenides such as sulfides (eg CdS, ZnS, PbS and Ag ₂ S), selenides (eg GaSe, CdSe and ZnSe) and tellurides Tellurides (eg ZnTe or CdTe); Halides (halides), for example, AgCl, AgBr, AgI, CuCl, CuBr, CdI 2 , and PbI _2; Carbides such as CdC ₂ or SiC; Arsenides such as AlAs, GaAs and GeAs; Antimonides such as InSb; Nitrides such as BN, AlN, Si ₃ N ₄ and Ti ₃ N ₄ ; Phosphides such as GaP, InP, Zn ₃ P ₂ and Cd ₃ P ₂ ; Phosphates, silicates, zirconates, aluminates, stannates, and corresponding mixed oxides (Y- or Eu-containing compounds); Luminescent pigments, spinels, ferrites or mixed oxides having a perovskite structure, for example BaTiO ₃ and PbTiO ₃ ).

Nanoscale inorganic solid particles are preferably Si, Ge, Al, B, Zn, Cd, Ti, Zr, Ce, Sn, In, La, Fe, Cu, Ta, Nb, V, Mo or W, more preferably Preferred are oxides or oxide hydrates of Si, Al, B, Ti and Zr. Especially preferred are oxides or oxide hydrates. Preferred nanoscale inorganic solid particles are SiO ₂ , Al ₂ O ₃ , ITO, ATO, AlOOH, Ta ₂ O ₅ , ZrO ₂ and TiO ₂ , with SiO ₂ being particularly preferred.

These nanoscale particles can be prepared in a conventional manner, such as, for example, pyrolysis, plasma methods, colloid techniques, sol-gel processes, controlled nucleation and growth. It can be produced by controlled nucleation and growth processes, MOCVD method and emulsion methods. These methods are described comprehensively in the literature. The sol-gel method is described in detail below.

The particles can be used directly in powder form or as a dispersion in a dispersant. Examples of commercially obtainable dispersions include aqueous silica sol from Bayer AG (Levasils®), and also colloidal organic sol from Nissan Chemicals (IPA-ST, MA -ST, MEK-ST, MIBK-ST). Powders obtainable are, for example, pyrogenic silica (from Aerosil) from Degussa.

Nanoscale solid particles have an average particle diameter (volume average, measurement: X-ray or, optionally, x-ray, or dynamic light scattering (Ultrafine Particle Analyzer) (UPA), usually 1 μm or less, generally 500 nm or less. The solid particles preferably have an average particle diameter of 300 nm or less, preferably 200 nm or less, especially 50 nm or less and more than 1 nm, preferably more than 2 nm, for example 1 to 20 nm. It can be used in the form of a powder, but is preferably used in the form of a sol or suspension.

Nanoscale solid particles used according to the invention are solid particles modified by organic surface groups, wherein the organic surface groups are groups having active hydrogen or precursors thereof, in particular hydroxyl groups and / or Epoxy group. Surface modification of such nanoscale solid particles is a known method and is disclosed, for example, in WO 93/21127 (DE 4212633), WO 96/31572 or WO 98/51747 (DE 19746885). With regard to the nanoscale solid particles and the surface modification thereof, all these documents can be referred to.

The preparation of the surface-modified nanoscale particles can generally be carried out in two different ways, firstly by surface modification of the already prepared nanoscale solid particles, and secondly with moieties suitable for the surface modification. It can be carried out by preparing the nanoscale solid particles using the above compound. These two routes are illustrated in detail in the above-mentioned patent applications.

Surface modifiers that are particularly suitable for surface modification of existing nanoscale particles include, as surface modifiers, reactive groups (attachment groups) present on the surface of the nanoscale solid particles. Compounds having at least one group capable of reacting or at least interacting, and then at least one group having active hydrogen or precursors thereof, in particular at least one hydroxyl or epoxy group, preferably of low molecular weight All of the compounds. For example, the surface groups present on the nanoparticles may be reactive groups having residual valences, for example hydroxyl groups and oxy groups for metal oxides, thiol groups and thio groups for metal sulfides, or In the case of nitrides they are amino, amide and imide groups.

The nanoscale particles can be surface modified by, for example, mixing the particles with a suitable surface modifier illustrated below, optionally in the presence of a catalyst in a solvent. In the case of silane as surface modifier, the modification is sufficient, for example, to stir the nanoscale particles for several hours at room temperature. Of course, suitable conditions, such as temperature, quantitative ratio, duration of reaction, etc., will vary depending on the particular reactant in each case and the degree of application desired.

The surface modifier may form, for example, covalent or ionic (such as salt) bonds, or coordinating bonds with the surface of the nanoscale solid particles, but among the pure interactions dipole-dipole interactions, hydrogen bonds and half Der Waals interaction is exemplified. Formation of covalent, ionic and / or coordinating bonds is preferred. Coordination bonds are understood to mean complex formation. Bronstead or Lewis acid / base reactions, complex formation or esterification may occur between the surface modifier and the particles.

According to the invention, it is also preferred that the surface modifier has a relatively small molecular weight. For example, the molecular weight may be less than 1500, in particular 1000 or less, preferably 500 or less or 400 or even 300 or less. This does not, of course, explicitly exclude the larger molecular weights of the compounds (eg up to 2000 moles and more).

In addition, the surface modifiers in particular have functional groups or precursors thereof with active hydrogen. It is known that isocyanates can react with groups with active hydrogens. Attachment of H-active groups or their precursors to nanoparticles by surface modifiers enables crosslinking reactions between nanoparticles and isocyanates upon curing.

Is the group having active hydrogen is preferably a hydroxyl group (-OH), thiol group (-SH), amino group (-NHR ', wherein R' is for example H, alkyl, especially C _{1 -4} - alkyl, cycloalkyl, for example, cyclohexanone carbonyl, aryl, especially C _{6 -10} - aryl, such as phenyl and naphthyl, and the corresponding aralkyl (aralkyl), and alkaryl (alkaryl) groups, such as tolyl and benzyl Or a carboxyl group (-COOH). The reaction product formed in the reaction with isocyanates is urethane (in the case of hydroxyl and carboxyl), thiourethane (in the case of thiols) or urea (in the case of amines).

Precursors of groups with active hydrogens in the present invention refer to groups that can be converted into groups with active hydrogens in the composition before or during curing. Important examples of such precursors are epoxy groups and carboxylic anhydride groups, which can be converted into hydroxyl groups and carboxyl groups, respectively, for example by hydrolysis reactions. The conversion of the epoxy groups to hydroxyl groups is described in more detail below.

Suitable surface modifiers for surface modification by groups with active hydrogen or organic radicals with precursors are surface modifiers with attachment groups for attachment to nanoparticles and should, of course, be selected according to the chemistry of the nanoparticles. In addition, the surface modifiers have at least one group or precursor thereof having active hydrogen as a functional group.

Particularly preferably used epoxy groups are precursors which can be converted into hydroxyl groups in the composition so that they can be used for the formation of urethane bonds which proceed in the curing step, either before or during curing (ie epoxy groups are converted in the composition). Can be). The conversion can be carried out, for example, by hydrolysis. To this end, for example, water or other compounds with active hydrogen atoms, and optionally catalysts (eg acids or bases) may be present in the composition. The epoxy groups, if present, can be converted to hydroxyl groups, especially before or during curing, and then reacted with isocyanates to form urethane bonds. The conversion of the epoxy groups to hydroxyl groups can occur, for example, immediately after surface modification has been carried out, or just before or during curing, for example after applying the composition to a substrate or introducing it into a mold. . The conversion to the hydroxyl group can be initiated by heating, for example. Those skilled in the art are familiar with the switching means and can select conditions such that the switching occurs at the desired time. This also applies to other precursors, especially anhydride groups as precursors to carboxyl groups.

Attachment groups included in the modifier include, for example, carboxylic acid groups, acid chloride groups, ester groups, nitrile and isonitrile groups, OH groups, SH groups, epoxy groups, anhydride groups, amide groups, primary, secondary and tertiary groups. CH-acidic moieties such as amino groups, Si-OH groups, hydrolyzable residues of silanes (SiX groups exemplified below), or β-dicarbonyl compounds. The attachment groups used are, for example, hydrolyzable groups of carboxylic acid radicals and in particular silanes, which of course are selected depending on the nature of the nanoparticles used.

Preferred surface modifiers are hydrolyzable silanes, so that the nanoscale solid particles are preferably groups having active hydrogens or precursors thereof, preferably epoxy or hydroxyl groups, thiol groups on unhydrolyzable substituents. , Surface modified with hydrolyzable silanes having amino groups or carboxyl groups or carboxyl anhydride groups.

Preferred surface modifiers are therefore silanes having epoxy silanes and at least one hydroxyl group. Silanes having hydroxyl groups often have a tendency to condense through transesterification and are not very stable, so it is preferable to use epoxy silanes. Thus, in a preferred embodiment, the organic radicals having hydroxyl or epoxy groups are derived from surface modification with silanes having epoxide groups on non-hydrolyzable substituents.

The silane is preferably at least one silane of formula (I):

Rh (R) _b SiX _(3-b)

Where

Rh radicals represent non-hydrolyzable substituents having epoxy groups or hydroxyl groups,

R radicals are the same or different and are non-hydrolyzable substituents of one another,

The X radicals are the same or different and each is a hydrolyzable group or a hydroxyl group,

b is 0, 1 or 2.

The b value is preferably 0, ie the silane preferably has the formula RhSiX ₃ .

In Formula I, the hydrolyzable X groups may be the same or different from one another, for example hydrogen, hydroxyl or halogen (F, Cl, Br or I), alkoxy (preferably C _1-6 -alkoxy, for example Methoxy, ethoxy, n-propoxy, i-propoxy and butoxy), aryloxy (preferably C _{6-10 -aryloxy} such as phenoxy), acyloxy (preferably C _{1 -6-} acyloxy, for example acetoxy or propionyloxy), alkylcarbonyl (preferably C _{2 -7-alkylcarbonyl,} such as acetyl), amino, preferably from 1 to 12 carbon atoms, especially 1 to 6 monoalkylamino or dialkylamino. Preferred hydrolyzable radicals are halogen, alkoxy groups and acyloxy groups. Particularly preferred hydrolysable radicals are C _{1 -4} - alkoxy groups, especially methoxy and ethoxy.

The non-hydrolyzable R radicals may be non-hydrolyzable R radicals with functional groups or non-hydrolyzable R radicals without such functional groups. As described, the R radical is preferably not present in the silane. It is preferred to have no functional groups when present.

Non-hydrolysable radical R of general formula I, for example, alkyl (e.g. C _{1 -20} - alkyl, especially C _{1 -4} - alkyl, such as methyl, ethyl, n- propyl, i- propyl, n- butyl , i- butyl, sec- butyl and tert- butyl), alkenyl (e.g. C _{2 -20} - alkenyl, in particular C _{2 -6} - alkenyl, such as vinyl, 1-propenyl and 2-propenyl phenyl), alkynyl (e.g., C _{2 -20} - alkynyl, in particular C _{2 -4} - alkynyl, for example, acetyl alkylenyl (acetylenyl) or propargyl (propargyl)), aryl (especially C _6-10 - Aryls such as phenyl and naphthyl), and corresponding aralkyl and alkaryl groups such as tolyl and benzyl, and cyclic C ₃ -C ₁₂ -alkyl and -alkenyl groups such as cyclopropyl , Cyclopentyl and cyclohexyl. The R and X radicals may each optionally have one or more typical substituents, for example halogen or alkoxy.

Non-hydrolyzable R radicals having such functional groups are for example ether, dialkylamino, optionally substituted aniline, amide, acryloyl, acryloyloxy, methacryloyl, methacryloyloxy, cyano as functional groups , Alkoxy, aldehyde, alkylcarbonyl and phosphoric acid groups. The functional group is bonded to the silicon atom via an alkylene, alkenylene or arylene bridging group, which is blocked by oxygen or an -NH- group (H may also be substituted with an alkyl group). Can be interrupted. The bridging group preferably contains 1 to 18, preferably 1 to 8, in particular 1 to 6 carbon atoms.

The aforementioned divalent bridging groups and optional substituents are present as in the case of alkylamino groups, for example derived from the aforementioned monovalent alkyl, alkenyl or aryl radicals. The R radical may of course also have one or more functional groups.

The Rh radical is a non hydrolyzable substituent having an epoxy group or a hydroxyl group. Rh corresponds to the R group wherein the functional group is an epoxy or hydroxyl group, and therefore everything described for R above applies accordingly. Examples of non-hydrolyzable Rh radicals having epoxy groups are epoxy- or glycidyloxy- (C _1-20 ) -alkyl radicals such as β-glycidyloxyethyl, γ-glycidyloxy Propyl, δ-glycidyloxybutyl, ε-glycidyloxypentyl, ω-glycidyloxyhexyl, epoxybutyl, epoxypropyl and 2- (3,4-epoxycyclohexyl) -ethyl, or hydroxyl- (C _{1 -20)} - alkyl radical, wherein the alkyl radical may be (interrupted) blocked by an amino group optionally substituted. γ-glycidyloxypropyl is particularly preferred.

Preferred compounds are γ-glycidyloxyalkyltrialkoxysilanes, epoxyalkyltri (m) ethoxysilanes or 2- (3,4-epoxy-cyclohexyl) alkyltri (meth) ethoxy Silane (2- (3,4-epoxy-cyclohexyl) alkyltri (m) ethoxysilanes) ((meth) ethoxy = methoxy or ethoxy), wherein the alkyl group may have 2 to 6 carbon atoms. Specific examples of corresponding silanes include γ-glycidyloxypropyltrimethoxysilane (GPTS), γ-glycidyloxypropyltriethoxysilane (GPTES), 3,4-epoxybutyltrimethoxysilane, 2- (3,4-epoxycyclohexyl) ethyltrimethoxysilane, hydroxymethyltriethoxysilane, bis (hydroxyethyl) -3-aminopropyltriethoxysilane and N-hydroxyethyl-N-methylaminopropyl -Triethoxysilane. Particularly suitable silanes of the formula I according to the invention are γ-glycidyloxypropyltrimethoxysilane (GPTS) and γ-glycidyloxypropyltriethoxysilane (GPTES).

Suitable for introducing amino, thio or carboxyl or carboxylic anhydride groups in a corresponding manner are at least one silane of the formula (la)

Ra (R) _b SiX _(3-b)

Where

Ra radicals represent non-hydrolyzable substituents having amino (for example -NHR 'groups as defined above), thio or carboxyl or carboxylic anhydride groups,

R, X and b are each as defined in formula (I).

Ra corresponds to the R group of formula (I) wherein the functional group is an amino, thio or carboxyl or carboxylic anhydride group, so that everything described for R in formula (I) applies accordingly.

Specific examples of the aminosilane include 3-aminopropyltriethoxysilane, 3-aminopropyltrimethoxysilane, N-2-aminoethyl-3-aminopropyltrimethoxysilane, trimethoxysilylpropyldiethylenetriamine, N- (6-aminohexyl) -3-aminopropyltrimethoxysilane, 4-aminobutyltriethoxysilane, (aminoethylaminomethyl) phenylethyltrimethoxysilane and aminophenyltrimethoxysilane.

Specific examples of thiosilanes (mercaptosilanes) include 3-mercaptopropyltrimethoxysilane, 3-mercaptopropyltriethoxysilane, 3-mercaptopropylmethyldimethoxysilane, 2-mercaptoethyltrie Methoxysilane, 1,2-dimercaptoethyltrimethoxysilane and p-mercaptophenyltrimethoxysilane. For example further examples can be found in DE-A-40 25 866, which is incorporated herein by reference.

The anhydride group may be a radical derived from a carboxylic anhydride, for example succinic anhydride, maleic anhydride or phthalic anhydride, these being one of the abovementioned radicals, in particular C To a silicon atom via ₁ -C ₄ -alkylene. Examples include [3- (triethoxysilyl) propyl] succinic anhydride, (dihydro-3- (3-triethoxysilyl) propyl) -2,5-furandione and [3- (trimethoxysilyl) propyl ] Succinic anhydride.

Further examples and definitions for epoxysilanes, aminosilanes, mercaptosilanes and carboxysilanes or carboxylic anhydride silanes are described, for example, in DE-A-100 54 248 or WO 01/40394 (DE-A, incorporated herein by reference). -199 58 336).

Organic radicals having a group or precursor with active hydrogen contain one or more groups or precursor with active hydrogen; In a preferred embodiment, the surface modification produces organic radicals containing one or more groups or precursors with active hydrogen. Organic radicals having two or more groups with such active hydrogens are produced, for example, when the epoxysilane is condensed with one hydrolyzable radical on the nanoparticle and with a second epoxysilane with an additional hydrolyzable radical. do. This reaction proceeds further, whereby two or more epoxy groups on one organic radical, or two or more hydroxyl groups after conversion can be obtained. In this regard, mention may be made of the polyols, polythiols, polyamines or polycarboxyl radicals or precursors thereof on the nanoparticles in this preferred embodiment. Of course, it is possible to use surface modifiers or mixtures of different surface modifiers with two different functional groups, thus producing nanoparticles with organic radicals of different groups with active hydrogens, for example amino and hydroxyl groups. do.

In another embodiment, the nanoparticles may first be subjected to first surface modification, which forms new functional groups on their surface, thereby introducing organic radicals having groups having active hydrogen or precursors thereof. It may be attached with a second surface modifier. In this way, groups having active hydrogen or precursors thereof, in particular hydroxyl or epoxy groups, are indirectly applied to the nanoparticles to obtain a two layer structure. This additional process allows for higher variability. Thus, for example, it is possible to attach a surface modifier having a group having active hydrogen or a precursor thereof, wherein the surface modifier has no attachment group for any of the unmodified nanoparticles of interest and the first surface modifier Can be attached via the applied functional groups. For example, carboxylic acid groups as functional groups can be introduced to the surface with the first surface modifier, which can then be reacted with the polyol as the second surface modifier.

Surface modification by the first and second surface modifiers is carried out in exactly the same manner as the direct surface modifications described above, so that all of the above is correspondingly applied. (Secondary) surface modifiers having groups with active hydrogens are those described above. Suitable first surface modifiers are bifunctional compounds, one of which functional groups serving as attachment groups for the nanoparticles, and the second functional group which may serve for attachment of the second surface modifier. Examples of suitable attachment groups, molecular weights and types of attachment to nanoparticles are the same as described above for surface modifiers for surface modification by organic radicals having the group having the active hydrogen or its precursor. The functional group may also be selected from the groups disclosed for the attachment group, wherein the functional group and the attachment group are the same or different.

Examples of the first surface modifier used in another embodiment are the modifiers already disclosed for the direct attachment, but of course, surface modifiers without groups or active precursors having active hydrogen as functional groups can also be used. Examples of such are unsaturated carboxylic acids, β-dicarbonyl compounds, for example β-diketones or β-carbonylcarboxylic acids, ethylenically unsaturated amines, or amines with additional functional groups such as amino acids. Of course, the modifiers and the following modifiers can also be used for the direct attachment of the group having active hydrogen or its precursor (if containing these groups).

Examples of compounds used for surface modification include, for example, saturated or unsaturated mono- and polycarboxylic acids having 1 to 12 carbon atoms (eg acrylic acid, methacrylic acid, crotonic acid, citric acid, adipic acid, succinic acid, glutaric acid). Acids, oxalic acid, maleic acid and fumaric acid) and also their anhydrides, esters (preferably C ₁ -C ₄ -alkyl esters) and amides.

Examples of further suitable surface modifiers are of the formula NR ¹ R ² R ³ R ⁴⁺ X ^- wherein R ¹ to R ⁴ are each the same or different and are aliphatic, aromatic or alicyclic having from 1 to 12 carbon atoms, in particular from 1 to 8 carbon atoms. A group group, for example an alkyl group having 1 to 12 carbon atoms, especially 1 to 8, more preferably 1 to 6 carbon atoms (eg methyl, ethyl, n- and i-propyl, butyl or hexyl), and X ⁻ is acetate containing an inorganic or organic anion, for example, OH ^-, Cl ^-, Br ^- or I ^- a] quaternary ammonium salts; Mono- and polyamines, in particular the formula R ' _{3 - n} NH _n where n is 0, 1 or 2, and the R' radicals are each independently 1 to 12 carbon atoms, in particular 1 to 8 carbon atoms, more preferably 1 to 6 carbon atoms And an ethylene polyamine (eg ethylenediamine, diethylenetriamine, etc.) of an alkyl group of (eg methyl, ethyl, n- and i-propyl, butyl or hexyl); amino acid; immigrant; Β-dicarbonyl compounds having 4 to 12, especially 5 to 8, carbon atoms such as acetylacetone, 2,4-hexanedione, 3,5-heptanedione, acetoacetic acid and C ₁ -C ₄ -alkyl acetoacetate; And silanes, for example, hydrolyzable silanes having at least one non-hydrolyzable group of formula (I) or formulas (II) and (III) illustrated below (non-hydrolyzable radicals have functional groups).

The composition also includes isocyanates. This may be conventional isocyanates known to those skilled in the art. The isocyanate has one, two or more isocyanate groups; Or preferably have two or more isocyanate groups. The isocyanate can be for example aliphatic, cycloaliphatic, aromatic or heterocyclic, monocyclic or polycyclic.

The isocyanate serves to crosslink the surface-modified nanoparticles. The isocyanate is preferably used in blocked form to prevent the uncontrolled rapid reaction from starting. Selective deblocking by, for example, heating can be used to perform selective crosslinking of groups with active H, such as hydroxyl functional groups and isocyanate functional groups, to provide polyurethanes. .

Blocking of the isocyanate is a method known to those skilled in the art to reversibly degrade the reactivity of the isocyanate. In order to block the isocyanates, all conventional blocking agents such as acetone oxime, cyclohexanone oxime, methyl ethyl ketoxime, acetophenone oxime, benzophenone oxime, 3,5-dimethylpyrazole, 1,2,4- Triazoles, ethyl malonate, ethyl acetoacetate, ε-caprolactam, phenol, ethanol are useful, and 1,2,4-triazole is preferred according to the invention. The blocking can be performed without solvent by melting the blocking agent and adding isocyanate, as well as with the solvent by adding a catalyst at room temperature. Suitable aprotic solvents for this purpose are, for example, acetone, dioxane, ethyl acetate, butyl acetate or toluene.

The isocyanate may be isocyanatosilane or conventional organic polyisocyanate. The above is preferably isocyanatosilane. The isocyanatosilanes are, in particular, hydrolyzable silanes having isocyanate groups on non-hydrolyzable radicals, or condensates thereof. When monomeric isocyanatosilanes are used, bi- or polyfunctional condensates can be formed in situ in the composition.

The isocyanatosilanes are also preferably used in blocked form. Condensates are preferably prepared from said monomeric isocyanatosilanes by the sol-gel method described above. It is often common sense or indeed necessary to block the starting monomers in order to prevent side reactions from forming in the condensate.

The isocyanatosilanes are preferably one or more silanes of the formula (II), or condensates based on these isocyanatosilanes:

Ri (R) _b SiX _(3-b)

Where

Ri radicals represent non-hydrolyzable substituents having isocyanate groups,

R radicals are the same or different and are other non-hydrolyzable substituents,

The X radicals are the same or different and are hydrolyzable or hydroxyl groups,

b is 0, 1 or 2.

Substituents R and X are each as defined in formula (I), wherein R is preferably a non-hydrolyzable substituent without functional groups, more preferably an alkyl group having 1 to 10 carbon atoms, and X is preferably 1 to 10 carbon atoms Is an alkoxy group, preferably methoxy or ethoxy.

Ri corresponds to the R group, wherein the functional group is an isocyanate group, so that everything described for R above applies accordingly. Preferred examples of the non-hydrolyzable Ri radical having an isocyanate group is isocyanato - (C _{1 -12)} - alkyl radical, for example, 3-isocyanato propyl radical. Specific examples of the corresponding silane are 3-isocyanatopropyltri- (m) ethoxysilane and 3-isocyanatopropyldimethylchlorosilane.

The organic isocyanates are conventional polyisocyanates, for example monomeric polyisocyanates, polyisocyanate adducts, so-called modified polyisocyanates or mixtures thereof. The polyisocyanate preferably contains at least two isocyanate groups. These are known to those skilled in the art and are commercially available, and are also described, for example, in G. Oertel, Polyurethane Handbook, Hanser-Verlag 1993, and "Methoden der organischen Chemie" (Methods of organic chemistry) (Houben-Weyl), vol. 14/2, Thieme Verlag, 1963. The adduct has, for example, an average NCO functionality of 2-6, preferably 2.4-4. Mixtures of monomeric polyisocyanates and polyisocyanate adducts produce average functional groups, which may also be within the ranges described above.

The polyisocyanate adducts are, for example, those typically used as hardeners for two-component urethane coatings and described in "Lackharze: Chemie, Eigenschaften and Anwendungen" (Coating resins: chemistry). , properties and applications), Eds D. Stoye, W. Freitag, Hanser Verlag Munich, Vienna, 1996. These polyisocyanate adducts preferably contain isocyanurates, biurets, allophanates and / or uretdione groups, for example 2 to 6 average NCO functional groups, and also for example 5 to 30 It has an NCO content of weight percent. The polyisocyanate may also contain monomeric polyisocyanates and / or other polyisocyanate adducts having, for example, urethane, carbodiimide and / or iminooxadiazinedione structures. It may be for example a trimer (isocyanurate) of hexamethylene 1,6-diisocyanate having an average NCO functionality of 3 to 4 and an NCO content of 15 to 25% by weight.

The monomeric polyisocyanate is an isocyanate containing two or more isocyanate groups, preferably isocyanates containing two isocyanate groups. Examples of monomeric isocyanates containing 3 or more isocyanate groups include 4-isocyanatomethyloctane 1,8-diisocyanate and aromatic polyisocyanates such as triphenylmethane 4,4 ', 4 "-triisocyanate or Polyphenyl-polymethylene polyisocyanate.

Monomeric isocyanates containing two isocyanate groups are generally represented by the formula Z (NCO) ₂ , where Z is a bifunctional organic radical having a molecular weight of, for example, 50 to 1000, preferably 70 to 320. . Z is a bifunctional C ₄ -C ₄₀ hydrocarbon radical, preferably a bifunctional aliphatic C ₄ -C ₁₈ radical, a bifunctional alicyclic C ₄ -C ₁₅ radical, a bifunctional araliphatic C ₇ -C ₁₅ radical or Preference is given to diisocyanates which are difunctional aromatic C ₆ -C ₁₅ radicals.

Examples of suitable isocyanates are diisocyanates known from polyurethane chemistry such as 1,3-diisocyanatobenzene, tolylene 2,4- and 2,6-diisocyanate (TDI), hexamethylene 1,6- Diisocyanate (HMDI), diphenylmethane 4,4'- and 2,4-diisocyanate (MDI), naphthylene diisocyanate, xylylene diisocyanate, isophorone diisocyanate, paraphenyl diisocyanate, dicyclohexylmethane di Isocyanate, cyclohexyl diisocyanate, polymethylpolyphenyl isocyanate, dodeca-methylene 1,6-diisocyanate, 1,4-bis (isocyanatocyclohexyl) methane, pentamethylene diisocyanate, trimethylene diisocyanate, tri Phenylmethane diisocyanate and derived from these diisocyanates, for example isocyanurate, uretdione, allophanei Higher molecular weight polyisocyanates based on lute and non-uret. The isocyanates are for example Desmodur® and Baymidur® (from Bayer), CARADATE® (from Shell), TEDIMON® (Eni) Obtainable under the trade names of Enichem and LUPRANAT® from BASF.

The nanoparticles (without surface modification) may be present in the composition in a proportion of 1 to 40% by weight, preferably 10 to 30% by weight, based on the solids content of the composition. The nanoparticle / surface modifier weight ratio is generally from 1: 1 to 1: 7, preferably from 1: 1 to 1: 2. The molar ratio of (optionally blocked) isocyanate groups / groups with active hydrogens (particularly hydroxyl groups) is generally for example 1/9 to 8/2; It is preferred to select the ratio so that there is generally a stoichiometric ratio for the reactive groups (NCO / active H, for example NCO / OH, approximately 1, for example 0.9 to 1.1).

The composition may also include additives which are typically added to coating compositions or compositions for moldings, depending on industry, purpose and desired properties. Specific examples include organic and inorganic colored pigments comprising metal colloids in the nanoscale range as thixotropic agents, solvents or dispersants, other substrate-forming components, polyols, for example as carriers of optical functions. , Dyes, UV absorbers, lubricants, leveling agents, wetting agents, adhesion promoters and catalysts.

The solvent (dispersant) used may, for example, be a solvent customary for coating. Particularly preferred solvents are water, in particular deionized water. Suitable organic solvents are polar and nonpolar and aprotic solvents. Examples thereof include alcohols, preferably lower aliphatic alcohols (C ₁ -C ₈ alcohols) such as methanol, ethanol, 1-propanol, i-propanol and 1-butanol; Ketones, preferably aliphatic ketones such as acetone, methyl ethyl ketone and methyl isobutyl ketone; Esters such as 2-methoxypropyl acetate, butyl acetate and ethyl acetate; Ethers, preferably lower dialkyl ethers such as diethyl ether, cyclic ethers such as dioxane or THF; Or monoethers of diols having C ₁ -C ₈ alcohols, for example ethylene glycol or propylene glycol having C ₁ -C ₈ alcohols; Aromatic or aliphatic hydrocarbons such as hexane, heptane, petroleum ether, toluene and xylene; Amides such as dimethylformamide; And mixtures thereof. The protic solvent should have a boiling point below the unblocking temperature of the blocked isocyanate to minimize side reactions. Examples are aliphatic alcohols having 1 to 4 carbon atoms.

It is also possible to add organic polyols which carry out part of the crosslinking with the isocyanates, thus allowing direct control of the properties (eg flexibility) of the resulting layer or molding. The polyol increases the organic fraction in the composition. Its use can also be economically advantageous. The polyol compounds used may be simple diols, triols and higher alcohols. It can be aliphatic, cycloaliphatic or aromatic, for example. Examples of polyols that can be used include ethylene glycol, diethylene glycol, 1,2-, 1,3- and 1,4-butanediol, 1,5- and 2,4-pentanediol, 1,6- and 2,5- Hexanediol, 1,4-cyclohexanediol, glycerol, trimethylolethane, trimethylolpropane, 2,2-bis (4-hydroxyphenylpropane) (bisphenol A), trishydroxy-phenylethane, pentaerythritol and Polyethylene glycols.

The composition may comprise a catalyst for the urethane formation reaction or the corresponding reactions. Examples are tin compounds known from polyurethane chemistry (eg dibutyltin dilaurate, dibutyltin diacetate, tin octoate) or amines (eg triethylamine, quinuclidin, DABCO).

The composition may also comprise organically modified inorganic or pure inorganic polycondensates or precursors thereof as a matrix-forming component. In this case, after curing, a composition is obtained which produces a substrate of organically modified inorganic or purely inorganic polycondensate with cross-linked nanoscale solid particles via the contained polyisocyanate component (nanomer composite). ).

The organically modified inorganic or pure inorganic polycondensates can be obtained by hydrolysis and condensation by the sol-gel method of the hydrolyzable starting material. This can be done prior to the addition of additional components of the composition or in the presence of one or more components of the composition in situ.

The organically modified inorganic polycondensate or its precursor preferably comprises a polyorganosiloxane or its precursor. The organically modified inorganic polycondensates or precursors thereof may also contain organic radicals having functional groups. Coating compositions based on organically modified inorganic polycondensates are disclosed, for example, in DE 19613645, WO 92/21729 and WO 98/51747, which are incorporated herein by reference.

Said organically modified inorganic polycondensates or precursors thereof are preferably prepared by condensation by sol-gel methods of hydrolytic and hydrolyzable starting compounds. Precursor refers to prehydrolyzates and / or precondensates of hydrolyzable starting compounds which are particularly condensed to a low degree. In the sol-gel method, the hydrolyzable compound is hydrolyzed with water, optionally by heating or acidic or basic catalyst, and partially condensed. Not only can stoichiometric amounts of water be used, but smaller or larger amounts can also be used. The sol formed can be adjusted to the desired viscosity in the composition by suitable parameters such as degree of condensation, solvent or pH. Further details on the sol-gel method are described, for example, in C.J. Brinker, G.W. Scherer: "Sol-Gel Science-The Physics and Chemistry of Sol-Gel Processing", Academic Press, Boston, San Diego, New York, Sydney (1990).

The hydrolyzable starting compound is a compound having a hydrolyzable group and at least some, for example at least 10%, of these compounds suitably also comprise non-hydrolyzable groups. In the absence of using compounds having non-hydrolyzable groups, pure inorganic polycondensates are obtained. As a rule, silanes without isocyanate groups are condensed together with the isocyanatosilanes described above to obtain modified isocyanatosilane condensates.

The hydrolyzable starting compound having at least one non-hydrolyzable group to be used is preferably a hydrolyzable organosilane or an oligomer thereof. Thus it may be a polycondensate or a precursor thereof, obtainable by, for example, a sol-gel method based on one or more silanes of formula III or oligomers derived therefrom:

R _a SiX _(4-a)

Where

R radicals are the same or different and represent a non-hydrolyzable group,

The X radicals are the same or different and are a hydrolyzable group or a hydroxyl group,

a is 1, 2 or 3.

a is preferably 1.

The R and X radicals are as defined in formulas (I) and (II) above. The non-hydrolyzable R radicals which may be the same or different from each other may be non-hydrolyzable R radicals having functional groups, or preferably non-hydrolyzable R radicals without functional groups as described above.

It is also possible to use organically modified inorganic polycondensates or precursors thereof which have at least partially organic radicals substituted by fluorine. Such silanes are disclosed in detail in WO 92/21729. For this purpose, it is possible to use hydrolyzable silane compounds having at least one non-hydrolyzable radical, preferably having the formula IV:

Rf (R) _b SiX _(3-b)

Where

X and R are as defined in formula (I),

Rf is preferably a non-hydrolyzable group having 1 to 30 fluorine atoms bonded to a carbon atom separated from Si by at least 2 atoms, preferably an ethylene group,

b is 0, 1 or 2.

R is in particular a radical without functional groups, preferably alkyl groups such as methyl or ethyl.

Among the hydrolyzable starting compounds used in the preparation of the above organically modified inorganic polycondensates or precursors thereof, compounds which are optionally free of non-hydrolyzable groups can also be used. These are in particular compounds of glass- or ceramic-forming elements, in particular compounds of at least one metal M from Groups III to V, in particular Groups III and IV, and / or Groups II to V of the Periodic Table of the Elements. These are preferably hydrolyzable compounds of Si, Al, B, Sn, Ti, Zr, V or Zn, in particular compounds of Si, Al, Ti or Zr, or mixtures of two or more of these metals. It is also possible to use small amounts of other hydrolyzable monomer compounds (40 mol% or less, in particular 20 mol% or less) of the polycondensate as a whole, in particular the other hydrolyzable compounds are in particular of the Periodic Table I and II elements of the Periodic Table (e.g. Na, K, Ca and Mg) and elements of Group V to VIII transition metals (eg Mn, Cr, Fe and Ni). It is also possible to use a hydrolyzable compound of the lanthanide series element. When using hydrolyzable compounds with very high reactivity (eg aluminum compounds), it is recommended to use complexing agents which prevent spontaneous precipitation of the corresponding hydrolyzate after addition of water. WO 92/21729 specifies suitable complexing agents which can be used in the case of reactive hydrolyzable compounds. If only hydrolyzable compounds are used without non-hydrolyzable radicals, pure inorganic condensates are produced.

These compounds are especially of the formula MX _n where M is a metal as defined above, X is as defined in formula I, two X groups may be substituted by one oxo group, and n is the valence of the element And usually 3 or 4). Preferred are alkoxides of Si, Zr and Ti. Compositions based on hydrolyzable compounds with non-hydrolyzable groups and hydrolyzable compounds without non-hydrolyzable groups are disclosed, for example, in WO 95/31413 (DE 4417405), incorporated herein by reference.

Suitable further or single compounds free of non-hydrolyzable groups are, in particular, hydrolyzable silanes having, for example, the formula (V):

SiX ₄

Where

X is as defined in formula (I).

Specific examples include _{Si (OCH 3) 4, Si} (OC 2 H 5) 4, Si (On- or _{iC 3 H 7) 4, Si} (OC 4 H 9) 4, SiCl 4, HSiCl 3, Si (OOCC 3 H) ₄ is available. Among these silanes, tetramethoxysilane and tetraethoxysilane are particularly preferred. Often, polycondensates based on silanes of formula III, in particular alkyl trialkoxysilanes and silanes of formula V, are preferred.

Examples of hydrolyzable compounds of other metals M include Al (OCH ₃ ) ₃ , Al (OC ₂ H ₅ ) ₃ , Al (OnC ₃ H ₇ ) ₃ , Al (OiC ₃ H ₇ ) ₃ , Al (OC ₄ H ₉ ) ₃ , AlCl ₃ , AlCl (OH) ₂ , Al (OC ₂ H ₄ OC ₄ H ₉ ) ₃ , TiCl ₄ , Ti (OC ₂ H ₅ ) ₄ , Ti (OnC ₃ H ₇ ) ₄ , Ti ( OiC ₃ H ₇ ) ₄ , Ti (OC ₄ H ₉ ) ₄ , Ti (2-ethylhexoxy) ₄ , ZrCl ₄ , Zr (OC ₂ H ₅ ) ₄ , Zr (OnC ₃ H ₇ ) ₄ , Zr (OiC ₃ H ₇ ) ₄ , Zr (OC ₄ H ₉ ) ₄ , ZrOCl ₂ , Zr (2-ethylhexoxy) ₄ , and complexing radicals such as β-diketones and (meth) acryloyl radicals , BCl ₃ , B (OCH ₃ ) ₃ , B (OC ₂ H ₅ ) ₃ , SnCl ₄ , Sn (OCH ₃ ) ₄ , Sn (OC ₂ H ₅ ) ₄ , VOCl ₃ and VO (OCH ₃ ) ₃ Zr compound.

The composition is preferably used as a coating layer. When the composition is used as a coating composition, all conventional materials can be coated. Examples of suitable substrates are substrates made of metals, semiconductors, glass, ceramics, glass-ceramic, plastic, wood, paper or inorganic-organic composite materials. In the case of high temperature curable compositions, temperature stable substrates (stable for at least 15 minutes at < RTI ID = 0.0 > 130 C) < / RTI > such as metals, glass, ceramics or heat resistant plastics are suitably used.

Examples of metal substrates are copper, aluminum, brass, iron, steel and zinc. Examples of semiconductors are silicon, for example silicon in the form of a wafer, and an indium tin oxide layer (ITO layer) on glass. The glass used may be all conventional types of glass, for example silica glass, borosilicate glass or soda-lime silicate glass. Examples of plastic substrates are polycarbonates, polymethyl methacrylates, polyacrylates, polyethylene terephthalates. Particularly suitable substrates for optical or optoelectronic are transparent substrates, for example transparent substrates made of glass or plastic. The substrate can be pretreated, for example by washing, corona treatment or precoating (eg lacquer or metallized surface).

The composition can be applied to the substrate in any suitable manner. All conventional wet chemical coating methods can be used. Examples include spin-coating, dip-coating, knife-coating, spraying, squirting, casting, painting painting, flow-coating, knife-casting, slot-coating, meniscus-coating, curtain-coating, and There is a roll application.

Molded or coated substrates

a) mixing the surface modified nanoparticles with isocyanates, optionally adding the additives mentioned above to the composition,

b) the composition is applied to a substrate or introduced into a mold,

c) curing to form urethane, thiourethane or urea crosslinks

Obtained when the blocked isocyanate is used, unblocking of the isocyanate is carried out before or during the curing and when the surface modified nanoparticles contain an epoxy group or a carboxylic anhydride group. Are converted to hydroxyl groups and carboxyl groups, respectively.

The unblocking, converting and curing (crosslinking to form urethane bonds, etc.) can be carried out in conventional manner, for example by irradiating or heating. The required energy input is of course dependent on the particular compound used in each case and any catalyst present. In general, thermal curing (eg, above 100 ° C., preferably above 130 ° C.) is preferred.

During the curing step, unblocking and switching steps that may be required may also be performed. The above steps may also be carried out before the curing step. For example, the hydrolysis of the epoxide or anhydride can be carried out at lower temperatures, which are not sufficient for curing, optionally with the addition of a catalyst. If unblocked isocyanates are used, milder curing conditions are possible. Upon curing, crosslinking is carried out by the formation of bonds, especially urethane, thiourethane or urea bonds between nanoparticles and isocyanates.

The resulting coatings and moldings are particularly suitable for optical applications because of their high transparency and wear resistance. These can be used, for example, as optical elements or as transparent layers on optical elements. A particularly suitable field of use is the field of coating of lenses.

The following examples further illustrate the invention.

In an embodiment, SiO ₂ nanoparticles modified with 3-glycidoxypropyltriethoxysilane (GPTES) are reacted with blocked isocyanates. The blocked isocyanate is obtained by reacting 3-isocyanatopropyltriethoxysilane (ICPTES) with 1,2,4-triazole. Blockers are used in slightly excess stoichiometric amounts for complete conversion (1: 1.1). 1,2,4-triazole is first charged under a nitrogen atmosphere and melted at an oil bath temperature of 135 ° C. ICPTES is added slowly through a dropping funnel. The reaction time is 6 hours. The reaction is monitored by IR spectroscopy using an isocyanate band. To 2.5 g of 3-glycidoxypropyltriethoxysilane (9 mmol) with vigorous stirring of 1.25 g of Levasil® 200S / 30 (Bay Age, a 30% colloidal solution of silicon dioxide in water) Add. The suspension is stirred for 24 hours. 2.84 g of the triazole-blocked ICPTES (9 mmol) are then prehydrolyzed with 0.24 g of 0.1 N hydrochloric acid for 30 minutes and added to the suspension. 2.7 g of demineralized water is added to the mixture, thus the solids content of the sol is 39.6%. Theoretical SiO ₂ content in the solid state is 10% by weight. The coating material was applied to the aluminum sheet by a rotary coating technique and precured at 100 ° C. for 10 minutes and then completely cured at 180 ° C. for 30 minutes. The coating layer was hard and transparent; The layer thickness was 10 μm. The mechanical properties of the coating layer with 0 to 40% by weight SiO ₂ in the solid state were measured with the aid of microhardness and taper abrasion test (load per roll: 500 g, CS-10F roll, 1000 cycles). The layer thickness was 10-11 μm. The mechanical properties improved with increasing SiO ₂ content (Table 1).

Changes in Mechanical Properties with Increasing SiO ₂ Content system SiO ₂ content (% by weight in solid state) HU [N / ㎡] W _e [%] HU _plast [N / ㎡] Elastic Modulus [GPa] Taber wearer weight loss [mg] I 0 202 73 345 4.6 2.5 I-10 10 320 70 543 6.9 1.2 I-20 20 326 67 591 7.4 1.2 I-30 30 370 67 701 7.6 1.3 I-40 40 440 65 818 9.2 1.7

The system is characterized by excellent mechanical strength; Conventional urethane systems based on IPDI have been tested in taper wear test (see Baumbach, B., Dearth, M., Kuttner, RS, Noble, KL, FATIPEC Congress 1998, 24, A-405). Has a weight loss of 40 mg.

Claims (24)

Surface-modified nanoscale solid particles having on the surface organic radicals having a group having active hydrogen or a precursor thereof, and At least one isocyanate, wherein the isocyanate groups may be blocked such that the particles crosslink upon curing of the composition. The method of claim 1, A composition having active hydrogen or a precursor thereof is a hydroxyl group, an epoxy group, a thiol group, an amino group or a carboxyl group or a carboxylic anhydride group. The method of claim 2, A composition characterized in that the group having active hydrogen or a precursor thereof is a hydroxyl group or an epoxy group. 4. The method according to any one of claims 1 to 3, And wherein the nanoscale solid particles are surface modified with hydrolyzable silanes having epoxy or hydroxyl groups, thiol groups, amino groups or carboxyl groups or carboxylic acid anhydride groups on the non-hydrolyzable substituent. 4. The method according to any one of claims 1 to 3, Wherein the surface-modified nanoscale solid particles are treated with a first surface modifier followed by a second surface modifier that provides an organic radical having a group having active hydrogen or a precursor thereof. 4. The method according to any one of claims 1 to 3, The organic radical having a hydroxyl group or an epoxy group may be glycidoxypropyltrimethoxysilane, glycidoxypropyl-triethoxysilane, 3,4-epoxybutyltri (meth) ethoxysilane, or 2- (3 And 4-epoxycyclohexyl) ethyltri (meth) ethoxysilane. 4. The method according to any one of claims 1 to 3, Compositions characterized in that the nanoscale solid particles are inorganic nanoscale solid particles. 4. The method according to any one of claims 1 to 3, Compositions characterized in that the nanoscale solid particles are metal, oxidized or sulfided particles or semiconductor particles. The method of claim 8, A nanoscale particle is a composition characterized in that the metal oxide particles of SiO ₂ , Al ₂ O ₃ , ITO, ATO, AlOOH, Ta ₂ O ₅ , ZrO ₂ or TiO ₂ . 4. The method according to any one of claims 1 to 3, At least one isocyanate is blocked. 4. The method according to any one of claims 1 to 3, Isocyanate is an organic polyisocyanate or isocyanatosilane or a condensate thereof. 4. The method according to any one of claims 1 to 3, And a composition comprising an organic polyol. 4. The method according to any one of claims 1 to 3, And an organically modified inorganic polycondensate. 4. The method according to any one of claims 1 to 3, And a catalyst for the reaction between a group having active hydrogen and an isocyanate. 4. The method according to any one of claims 1 to 3, Wherein, when there is an organic surface radical having an epoxy group, the epoxy group can be converted to a hydroxyl group to form a urethane bond. 4. The method according to any one of claims 1 to 3, And wherein the nanoscale solid particles have, on the surface, organic radicals having at least two groups or active precursors having active hydrogens. The layer of molding or coated substrate is the cured composition as claimed in claim 1, wherein the epoxy groups or carboxylic anhydride groups (if any) present on the surface of the solid particles are for further reaction before or during curing. Moldings or coated substrates converted to hydroxyl groups and carboxyl groups, respectively. The method of claim 17, Molded or coated substrate comprising an optical device or a transparent layer on the optical device. The method of claim 17 or 18, A coated substrate wherein the substrate is made of metal, glass, plastic, wood or paper. The method of claim 17 or 18, A coated substrate wherein the substrate is a lens. a) surface-modified nanoscale solid particles having on the surface an organic radical having a group having active hydrogen or a precursor thereof, mixed with at least one isocyanate, provided that the isocyanate groups may be blocked, b) the resulting composition is applied to a substrate or introduced into a mold, and c) curing is carried out to form a bond between the group having an active hydrogen on the nanoparticles and an isocyanate, When using blocked isocyanates, the isocyanate is unblocked either before or during the cure, and when the surface-modified nanoparticles comprise a precursor, the precursor is converted to a group with active hydrogen, 19. Process for the production of molded articles or coated substrates as claimed in claim 17 or 18. The method of claim 21, The organic radical contains hydroxyl, epoxy groups, thiol groups, amino groups, carboxyl or carboxylic anhydride groups, and the organic radicals are cured to form urethane, thiurethane or urea crosslinks, Wherein if the surface-modified nanoparticles contain an epoxy group or a carboxylic anhydride group, the epoxy group is converted to a hydroxyl group and the carboxylic anhydride group to a carboxyl group. The method of claim 17 or 18, Molded or coated substrate, characterized in that it is used for optical applications. 4. The method according to any one of claims 1 to 3, A composition, characterized in that it is used to coat a substrate with an optically high-value layer.